EP3237533B1 - Composition à base de polyéthylène recyclé à partir de déchets de câble - Google Patents

Composition à base de polyéthylène recyclé à partir de déchets de câble Download PDF

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Publication number
EP3237533B1
EP3237533B1 EP15813427.0A EP15813427A EP3237533B1 EP 3237533 B1 EP3237533 B1 EP 3237533B1 EP 15813427 A EP15813427 A EP 15813427A EP 3237533 B1 EP3237533 B1 EP 3237533B1
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Prior art keywords
polyethylene
composition according
pex
polyethylene composition
composition
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German (de)
English (en)
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EP3237533A1 (fr
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Carl-Gustaf Ek
Åsa WANNERSKOG
Stefan Rieder
Franz Ruemer
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Borealis AG
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Borealis AG
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/003—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor characterised by the choice of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/02—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of definite length, i.e. discrete articles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J11/00—Recovery or working-up of waste materials
    • C08J11/04—Recovery or working-up of waste materials of polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/201—Pre-melted polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/04—Polymers of ethylene
    • B29K2023/06—PE, i.e. polyethylene
    • B29K2023/0691—PEX, i.e. crosslinked polyethylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2509/00—Use of inorganic materials not provided for in groups B29K2503/00 - B29K2507/00, as filler
    • B29K2509/06—Concrete
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/26—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/04—Homopolymers or copolymers of ethene
    • C08J2423/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/26—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/22—Mixtures comprising a continuous polymer matrix in which are dispersed crosslinked particles of another polymer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/06—Properties of polyethylene
    • C08L2207/062—HDPE
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/20—Recycled plastic
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/62—Plastics recycling; Rubber recycling

Definitions

  • the present invention relates to a new polyethylene composition which comprises at least one polyethylene obtained from recycled waste material. Furthermore, the present invention relates to a process for producing said polyethylene composition and the use of said composition in infrastructure, engineering applications and packaging applications.
  • post-consumer waste refers to objects having completed at least a first use cycle (or life cycle), i.e. having already served their first purpose; while industrial waste refers to the manufacturing scrap which does normally not reach a consumer.
  • first use cycle or life cycle
  • industrial waste refers to the manufacturing scrap which does normally not reach a consumer.
  • virtual waste denotes the newly- produced materials and/or objects prior to first use and not being recycled.
  • JP2002/080671 discloses a polyvinyl chloride-based recycled plastic composition obtained by mixing and melting covering plastics and sheaths of waste cables containing: (A) polyvinyl chloride and (B) polyethylene or silane-crosslinked polyethylene, with chlorinated polyethylene.
  • the abovementioned polyvinyl chloride-based resin is said to be useful for making cable sheaths.
  • JP2013045643 relates to insulated electric wire and cable which use a large amount of waste-derived recycled material which contains crosslinked polyolefin homopolymer.
  • the recycled fraction containing cross-linked material has a gel content of 40% or less and the recycled material is present in an amount of 75 wt% or more in respect of the total composition.
  • CN102898768 discloses a flame retardant TPE composition made from cross-linked polyethylene cable waste.
  • the amount of cross-linked cable waste is 40% or less and contains furthermore SBS block co-polymer (major part), phosphate flame retardants, extending oil, silane coupling agents and a very low amount of other auxiliaries.
  • the prepared TPE is provided with good flame retardance and other performances up to standards.
  • the waste streams containing crosslinked polyolefin, especially crosslinked polyethylene (PEX), are more often used for energy recovery (e.g. incineration in a district heating plant or for heat generation in the cement industry) but less recycled into new products.
  • energy recovery e.g. incineration in a district heating plant or for heat generation in the cement industry
  • a polyethylene composition characterized in that it comprises a base resin and an inorganic mineral filler which is present in the composition in an amount of 1 to 50 wt% in respect to the weight of composition, wherein said base resin comprises:
  • the polyethylene composition according to the invention has an improved balance between stiffness, as shown by their flexural modulus, and good ductility in terms of elongation at break as well as stress at break. Further, the composition shows a surprisingly good impact performance.
  • the composition in the present invention shows mechanical properties which at least have reduced the gap with the properties of virgin polyethylene.
  • base resin denotes the entirety of polymeric components in the polyethylene composition according to the invention.
  • the base resin can comprise additional polymer components.
  • the base resin consists of the first crosslinked polyethylene (PEX) and the second polyethylene (PE).
  • crosslinked polyethylene (PEX) can be described and measured by its gel content.
  • the crosslinked polyethylene (PEX) in the present invention can be referring to a polyethylene composition comprising a fraction (A1) of fully crosslinked polyethylene and a fraction of non-crosslinked thermoplastic polyethylene (A2).
  • the fully crosslinked polyethylene A1 generally has a gel content in the range of 50% to 80%, preferably in the range of 55% to 70%, based on the weight of fraction A1.
  • the gel content of the crosslinked polyethylene (component A) is generally in the range of 5% to 80%, preferably in the range of 20% to 65%, more preferably in the range of 40% to 60% while being measured in respect of the total weight of PEX.
  • the fraction A1 has a weight percentage of between 20% and 100%, suitably of between 25% and 90%, more suitably of between 30% and 80%, based on the weight sum of A1 and A2.
  • the PEX is obtained from recycled waste.
  • the PEX can be either recycled post-consumer waste, industrial PEX waste from the cable manufacturing process, or alternatively, a combination of both.
  • the PEX in the present invention is obtained from recycled waste by means of plastic recycling processes known in the art.
  • said product may be obtained by means of a recycling process referred to as "PlastSep", which originally is developed by a company in the NKT group and described in the reference document " 'New Technology for Recycling of Plastics from Cable Waste', Paper presented at 8th International Conference on Insulated Power Cables, Why, 19-23 June 2012, by Annika Boss et al.” More preferably, the PEX obtained from this kind of process is generally in the form of granules with a diameter of less than 1mm.
  • the second polyethylene is a non-crosslinked thermoplastic polyethylene, which enables good processability and good compounding results with the crosslinked polyethylene (PEX).
  • the second polythylene can be selected from virgin polyethylene, recycled thermoplastic polyethylene or a mixture thereof.
  • the inorganic filler is an essential part of the composition according to the invention. Fillers are generally added to improve the mechanical properties, in particular the E-modulus.
  • additives for use in the composition are pigments or dyes (for example carbon black), stabilizers (anti-oxidant agents), anti-acids and/or anti-UVs, antistatic agents and utilization agents (such as processing aid agents)
  • the amount of these additives is in the range of 0-8 wt%, preferably in the range of 0-5 wt%, more preferably in the range of 0.01 to 3 wt%, based on the weight of total composition.
  • the weight ratio of PEX to PE in the base resin is in the range of higher than 10:90 to 90:10, preferably in the range of 10:90 to 70:30, more preferably in the range of 10:90 to 50:50.
  • the crosslinked polyethylene (PEX) is obtained from the recycled material from electrical cable waste. More preferably, the PEX is obtained from recyclates of the high voltage (HV) and medium voltage (MV) power cable waste.
  • the electrical cable waste is mainly a mixture of various compositions including PE or PEX based compositions and PVC based compositions. Therefore after the separating step in the recycling process, a certain level of contamination caused by the PVC is probably present in the recycled PEX. This contamination leads to higher chlorine content in the recycled PEX, compared to the normal chlorine content in virgin polyethylene, especially the chlorine level in low pressure polymerized PE such as LLDPE, MDPE and HDPE, where the chlorine level is due to remaining catalyst residues.
  • the crosslinked polyethylene (PEX) has a chlorine content in the range of 100 to 5000 ppm, preferably of 200 to 4000 ppm, most preferably of 300 to 2000, measured with X-ray fluorescence analysis (XRF).
  • XRF X-ray fluorescence analysis
  • the crosslinked polyethylene has a copper content in the range of 20-500 ppm, more preferably in the range of 30 to 250 ppm, and/or an aluminum content in the range of 500-15000 ppm, more preferably in the range of 1000-10000 ppm, measured with X-ray fluorescence analysis (XRF).
  • XRF X-ray fluorescence analysis
  • the second polyethylene (PE) in the present invention is selected from virgin high density polyethylene (vHDPE), virgin medium density polyethylene (vMDPE), recycled high density polyethylene (rHDPE), recycled medium density polyethylene (rMDPE) and the mixtures thereof.
  • vHDPE virgin high density polyethylene
  • vMDPE virgin medium density polyethylene
  • rHDPE recycled high density polyethylene
  • rMDPE recycled medium density polyethylene
  • PE when PE is selected from virgin PE, it has a density of equal to or higher than 0.925 g/cm 3 , more preferably equal to or higher than 0.945 g/cm 3 ; when PE is selected from recycled PE, it comprises more than 80%, preferably more than 90% of polyethylene having a density of not lower than 0.925 g/cm 3 , more preferably not lower than 0.945 g/cm 3 .
  • inorganic mineral filler is present in an amount of at least 1 wt. %, more preferably at least 5 wt. %, still more preferably at least 8 wt. %, still more preferably at least 10 wt.% and most preferably at least 12 wt.%. Furthermore, in the composition inorganic filler is present in an amount of at most 50 wt.%, more preferably of at most 45 wt.%, still more preferably at most 40 wt.%.
  • inorganic mineral filler is present in a range of 1-50 wt%, preferably 5-45 wt%, more preferably 8-42 wt%, most preferably 10-40 wt%.
  • the filler of the composition according to the invention may comprise all inorganic filler materials as known in the art.
  • the filler may also comprise a mixture of any such filler materials. Examples for such filler materials are oxides, hydroxides and carbonates of aluminum, magnesium, calcium and/or barium.
  • the filler comprises an inorganic compound of a metal of groups 1 to 13, more preferred groups 1 to 3, still more preferred groups 1 and 2 and most preferred group 2, of the Periodic Table of Elements.
  • the inorganic filler comprises a compound selected from carbonates, oxides and sulphates.
  • Preferred examples of such compounds are calcium carbonate, talc, magnesium oxide, huntite Mg 3 Ca(CO 3 ) 4 , and hydrated magnesium silicate, and kaolin ("China clay"), with particularly preferred examples being calcium carbonate, magnesium oxide, hydrated magnesium silicate, and kaolin ("China clay").
  • the inorganic filler has a weight average mean particle size, D50, of 25 micron or below, more preferably of 15 micron or below.
  • D50 weight average mean particle size
  • the filler has a particle size of 40 microns or higher, more preferably only 2 wt% of the filler has a particle size of 30 micron or higher.
  • the particles have a weight average mean particle size D50 of 6 micron or below, more preferably of 4 micron or below.
  • the weight percentage of the filler in the total composition is preferred to be in the range of 20-45%.
  • preferably only 2 wt% has a particle size of 8 micron or more, more preferably of 7 micron or more.
  • the weight percentage of the filler in the total composition is preferred in the range of 5-30%.
  • the purity of the filler is 94 % or higher, preferably is 95 % or higher and more preferably 97 % or higher.
  • the inorganic filler may comprise a filler which has been surface-treated with an organosilane, a polymer, a carboxylic acid or salt etc. to aid processing and provide better dispersion of the filler in the organic polymer.
  • Such coatings usually do not make up more than 3 wt% of the filler.
  • the polyethylene composition in the present invention is generally having a gel content in the range of 5-50 wt%, preferably 7-40 wt%, more preferably 10-40 wt% in respect to the weight of the base resin as measured according to ASTM D 2765:2006.
  • composition according to the invention has a good balance of stiffness and ductility as compared to prior art materials. It should be noted that the composition in the present invention is characterized not by any single one of the defined mechanical property features, but by their combination. By this combination of features it can advantageously be used in many application fields.
  • the polyethylene composition is therefore characterized in that it has a flexural modulus determined according to ISO 178 of more than 840 MPa, preferably more than 1000 MPa, more preferably more than 1100 MPa and more than 1200MPa.
  • composition according to the present invention is further characterized in that it has an elongation at break determined according to ISO 527-2 of more than 2%, preferably more than 3%, more preferably more than 4%, most preferably more than 5%.
  • composition in the present invention preferably has a tensile stress at break determined according to ISO 527-2 of more than 13 MPa, preferably more than 14MPa, more preferably more than 15MPa, most preferably more than 16MPa.
  • composition in the present invention preferably has a yield stress determined according to ISO 527-2 of more than 15 MPa, preferably more than 17MPa, more preferably more than 19MPa, most preferably more than 20MPa.
  • an additional dry mixing step of all components can be applied prior to the melted homogenizing step.
  • the melt temperature at the outlet of the compounding unit is around 180-220 °C for polyethylene compounds in order to create a sufficient mixing effect.
  • the melt temperature at the outlet of the homogenization unit could however be both higher and lower depending on the needs. Particularly for compounds which are difficult to disperse and homogenize, the outlet temperature could be as high as 300 °C.
  • the homogenization would take place below around 180 °C and lower, e.g. at 170 °C or 160 °C or even lower.
  • the target would be to make the compounding step with an as low as possible melt temperature for keeping the cost of the product low, to increase the sustainability effort and for minimizing the additional odour and smell that is often generated with recyclate containing compounds at high temperatures from e.g. contaminating ingredients in the recyclate.
  • the PEX, PE and the inorganic filler and, optionally, other additives or other polymer components can be added to the inlet hopper of a compounding unit.
  • the compounding unit could also be equipped with more than one inlet, e g. two inlets, and e.g. all the polymeric ingredients, optionally with additives/antioxidants, could be fed in the first inlet and the filler fed in the 2nd inlet further downstream the unit.
  • all the polymers optionally with additives/antioxidants could be fed in the first inlet including part of the filler portion and the remaining part of the filler to be fed into the 2nd inlet further downstream.
  • the compounding unit could be any conventionally used compounding or extruder unit, preferably a co-rotating or counter-rotating twin screw extruder, or an internal mixer such as a Banbury type mixer or single crew extruder such as a Buss co-kneader or a conventional single screw extruder.
  • Static mixers such as Kenics, Koch etc can also be used in addition to the compounding or extruder units mentioned in order to improve the distribution of the filler in the polymer matrix.
  • the extruder or compounding unit is equipped with one or more vacuum degassing units along the screw or screws, with or without the use water stripping units.
  • the function of a water stripping unit is to add small amounts of water into the melt upfront of a mixing and a decompression and vacuum degassing section. The resultant of this is to bring down both the smell and odour, as well as reducing the amount of volatiles in the final compound.
  • the present invention is related to the use of a polyethylene composition as described hereinbefore for reducing the carbon foot print of the articles that are originators of the PEX. This is especially advantageous in the field of infrastructure, engineering applications and packaging.
  • the present invention is related to the use of the polyethylene composition according to the invention for reducing the carbon foot print in the production of pipes and cables, traffic and construction elements as well as packaging materials.
  • the present invention is related to the use of the polyethylene composition according to the invention for reducing the carbon foot print in the production of objects listed below:
  • Gel Content is measured according to ASTM D2765-90 using a sample consisting of the polyethylene composition of the invention (Method A, decaline extraction).
  • X-ray Fluorescence analysis The elemental content was analysed by wavelength dispersive XRF (AXS S4 Pioneer Sequential X-ray Spectrometer supplied by Bruker). The pellet sample was pressed to a 3 mm thick plaque (150°C for 2 minutes, under pressure of 5 bar and cooled to room temperature). Generally, in XRF method, the sample is irradiated by electromagnetic waves with wavelengths 0.01 -10 nm. The elements present in the sample will then emit fluorescent X-ray radiation with discrete energies that are characteristic for each element. By measuring the intensities of the emitted energies, quantitative analysis can be performed. Here, the analysis has been done with a standard-free program where the 28 most common elements are detected and the concentrations of the detected elements are calculated based on a CH 2 matrix.
  • Flexural modulus is determined on compression molded sample according to ISO 178 at 23°C, the sample thickness is mentioned below in the sample preparation.
  • Tensile testing Tensile stress and modulus for the examples IE1-5, CE3-5 were determined on compression moulded specimens according to ISO 527-2 at 50 mm/min and 23°C, the sample thickness is mentioned below in the sample preparation.
  • Tensile test for the examples IE6 and CE1, 2, 6-8 was measured according to ISO 527-2 on injection moulded specimens as described in EN ISO 1872-2 (80 x 10 x 4 mm), wherein the crosshead speed for testing the modulus was 1mm/min and crosshead speed for testing the tensile strength and elongations was 50 mm/min.
  • Test specimen produced as described in EN ISO 1872-2 (the produced test specimens were 10 multipurpose test specimen of type B according to ISO 3167).
  • Charpy impact test The charpy notched impact strength (Charpy NIS) is measured according to ISO 179 1eA at 23 °C and -20 °C respectively. The impact is measured on samples prepared from injection molded specimens as described in EN ISO 1872-2 (80 x 10 x 4 mm)
  • PEX RECYCLATE 1MM a crosslinked polyethylene which is entirely recycled post-consumer cable waste is in the form of granules smaller than 1 mm in diameter.
  • the PEX has a gel content of about 50 wt%.
  • Table 1 shows the analytical result of PEX RECYCLATE 1MM Table 1. Elemental content determined by XRF analysis on three pressed 3 mm plaques.
  • HE3450 a virgin high density polyethylene bimodal copolymer, commercially available from Borealis with a melt flow rate (MFR2) of 0.5 g/10min, according to ISO 1133 (190 °C, 2.16 kg) and a density of 0.950 g/cm 3 .
  • MFR2 melt flow rate
  • KRUTENE-HD a recycled high density polyethylene in the form of pellets, commercially available from KRUSCHITZ GMBH with a melt flow rate (MFR2) of 0.49 g/10min, according to ISO 1133 (190 °C, 2.16 kg), and density of 0.950 g/cm 3 .
  • CALCITEC M/5 Calcium carbonate filler which had a weight average mean particle size D50 of 5.0 microns with only 1 wt% having a particle size of 19 micron or higher, and a purity of 99% CaCO 3 .
  • MISTRON 75-6 A Talc filler which has a weight average mean particle size D50 of 4.0 microns with only 2 wt% having a particle size of 20 micron or higher and a purity of 98% Mg-silicate.
  • the predetermined amount of PEX and PE was mixed with the inorganic filler in a Brabender 350E mixer with a roller element at a temperature of 180°C for 10 min.
  • the screw speed was 40 RPM.
  • the equipment was purged with nitrogen during the homogenisation to minimise degradation.
  • Injection moulding The test specimens for the examples IE6 and CE1, 2, 6-8 were injection moulded using a machine Engel e-motion 310/55HL with a 35 mm screw at 210°C.
  • Compression moulding The test specimens for the examples IE1-5, CE3-5 were compression moulded. The raw materials were transferred to a compression moulding device to produce about 2-4 mm thick plates from which the samples were machined into the sample type specified for the particular test method, respectively. 2 mm thick samples were used for the tensile measurements and 4 mm thick samples were used for measurements in bending mode. Compression moulding conditions: 200°C at low pressure for 10 minutes and for 5 minutes at 614 N/cm 2 and cooling down at 15°C/min.
  • Table 2 and Table 3 list the composition recipes and mechanical properties for six inventive examples IE1 to IE6 and eight comparative examples CE1 to CE8.
  • the inventive examples show a surprisingly good combination of mechanical properties comparing to the CE2-8 examples and bring the mechanical properties closer to CE1.
  • Table 2 list the composition recipes and mechanical properties for six inventive examples IE1 to IE6 and eight comparative examples CE1 to CE8.
  • the inventive examples show a surprisingly good combination of mechanical properties comparing to the CE2-8 examples and bring the mechanical properties closer to CE1.
  • Table 2 list the composition recipes and mechanical properties for six inventive examples IE1 to IE6 and eight comparative examples CE1 to CE8.
  • the inventive examples show a surprisingly good combination of mechanical properties comparing to the CE2-8 examples and bring the mechanical properties closer to CE1.
  • Table 2 list the composition recipes and mechanical properties for six inventive examples IE1 to IE6 and eight comparative examples CE1 to CE8.
  • the inventive examples show a surprisingly good combination of mechanical properties comparing to the CE2-8 examples and bring
  • composition recipe and mechanical properties of the comparative samples CE1 CE2 CE3 CE4 CE5 CE6 CE7 CE8 HE3450-H (0.950 g/cm 3 ) 100 80 KRUTENE-HD (0.952 g/cm 3 ) 55 80 60 100 PEX RECYCLATE 1MM 60 75 45 CALCITEC M/5 40 40 MISTRON 75-6 A 20 25 20 sum 100 100 100 100 100 100 100 100 Stress at break (MPa) 23.1 4.6 10.7 10.2 6.6 5.3 13.0 8.5 Yield stress 19.6 - 11.9 10.5 18.1 - - - Flexural modulus (MPa) 820 - 590 400 620 - - - EAB (%) 647.0 82.0 8.4 8.9 63.8 53.0 13.9 144.0 Charpy NIS 23°C (kJ/m 2 ) 56.0 34.2 - - - 8.0 16.5 18.0 Charpy NIS -20°C (kJ/m 2 ) 16.9 10.4 - - - 3.9 5.8 4.0

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  • Chemical & Material Sciences (AREA)
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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Sustainable Development (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
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Claims (15)

  1. Composition de polyéthylène caractérisée en ce qu'elle comprend une résine de base et une charge minérale inorganique qui est présente dans la composition en une quantité de 1 à 50 % en poids par rapport au poids de la composition, dans laquelle ladite résine de base comprend :
    a) un premier polyéthylène réticulé (PEX) possédant une teneur en gel (mesurée conformément à la norme ASTM D 2765:2006) située dans la plage allant de 5 % à 80 % par rapport au poids du polyéthylène réticulé (PEX), ledit polyéthylène réticulé (PEX) étant obtenu à partir de déchets recyclés, et
    b) un deuxième polyéthylène (PE) choisi parmi le polyéthylène vierge et le polyéthylène recyclé, ainsi que leurs mélanges.
  2. Composition de polyéthylène selon la revendication 1, caractérisée en ce que le rapport en poids PEX/PE dans la résine de base est situé dans la plage allant de plus de 10/90 à 90/10.
  3. Composition de polyéthylène selon la revendication 1 ou 2, caractérisée en ce que le polyéthylène réticulé (PEX) est obtenu à partir de déchets recyclés, lesquels déchets sont choisis parmi les déchets de câbles électriques.
  4. Composition de polyéthylène selon l'une quelconque des revendications précédentes, caractérisée en ce que le polyéthylène réticulé (PEX) possède une teneur en chlore située dans la plage allant de 300 à 2000 ppm, mesurée par analyse de fluorescence aux rayons X (XRF).
  5. Composition de polyéthylène selon l'une quelconque des revendications précédentes, caractérisée en ce que le polyéthylène réticulé (PEX) possède :
    a) une teneur en cuivre située dans la plage allant de 20 à 500 ppm, et/ou
    b) une teneur en aluminium située dans la plage allant de 500 à 15000 ppm, mesurée par analyse de fluorescence aux rayons X (XRF).
  6. Composition de polyéthylène selon l'une quelconque des revendications précédentes, caractérisée en ce que le deuxième polyéthylène (PE) est choisi parmi le polyéthylène haute densité vierge (vHDPE), le polyéthylène moyenne densité vierge (vMDPE), le polyéthylène haute densité recyclé (rHDPE), le polyéthylène moyenne densité recyclé (rMDPE), et leurs mélanges.
  7. Composition de polyéthylène selon l'une quelconque des revendications précédentes, caractérisée en ce que la charge minérale inorganique est choisie parmi CaCO3 et le talc.
  8. Composition de polyéthylène selon l'une quelconque des revendications précédentes, caractérisée en ce que la composition possède une teneur en gel située dans la plage allant de 10 à 40 % en poids par rapport au poids de la résine de base, telle que mesurée conformément à la norme ASTM D 2765:2006.
  9. Composition de polyéthylène selon l'une quelconque des revendications précédentes, caractérisée en ce que la composition présente un module de flexion, déterminé conformément à la norme ISO 178, supérieur à 840 MPa.
  10. Composition de polyéthylène selon la revendication 9, caractérisée en ce que la composition présente de plus un allongement à la rupture, déterminé conformément à la norme ISO 527-2, supérieur à 2 %.
  11. Composition de polyéthylène selon la revendication 9 ou 10, caractérisée en ce que la composition présente de plus une contrainte de traction à la rupture, déterminée conformément à la norme ISO 527-2, supérieure à 13 MPa.
  12. Composition de polyéthylène selon l'une quelconque des revendications 9 à 11, caractérisée en ce que la composition présente de plus une contrainte à la limite élastique, déterminée conformément à la norme ISO 527-2, supérieure à 15 MPa.
  13. Procédé pour produire une composition de polyéthylène selon l'une quelconque des revendications 1 à 12, caractérisé en ce que ledit procédé comprend les étapes suivantes :
    a) introduction des ingrédients dans la trémie d'entrée d'une unité de combinaison ;
    b) combinaison des ingrédients, laquelle combinaison est mise en oeuvre par homogénéisation des ingrédients introduits dans l'entrée et élévation de la température au-delà du point de fusion de l'ingrédient polymère thermoplastique principal, ce qui donne un composé en mélange ;
    c) éventuellement refroidissement dudit composé en mélange et pastillage.
  14. Procédé pour produire un article façonné comprenant une composition de polyéthylène selon l'une quelconque des revendications 1 à 12, ou une composition de polyéthylène produite par le procédé selon la revendication 13, caractérisé en ce que ledit procédé comprend l'étape additionnelle de façonnage de ladite composition de polyéthylène au moyen d'une étape de moulage.
  15. Utilisation de la composition de polyéthylène selon l'une quelconque des revendications 1 à 12 dans le domaine des infrastructures, des immeubles et constructions, des applications d'ingénierie et des emballages, pour réduire le bilan carbone lors de l'étape de fabrication.
EP15813427.0A 2014-12-22 2015-12-18 Composition à base de polyéthylène recyclé à partir de déchets de câble Active EP3237533B1 (fr)

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CN108034105A (zh) * 2017-11-17 2018-05-15 神华集团有限责任公司 交联聚乙烯用组合物和交联聚乙烯及其制备方法
DE102018009171A1 (de) * 2018-11-22 2020-05-28 Bb Engineering Gmbh Verfahren und Vorrichtung zum Recyceln von Kunststoffen
JP6752935B1 (ja) * 2019-05-28 2020-09-09 旭化成株式会社 樹脂成形体の製造方法
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AU2015371394A1 (en) 2017-05-25
JP2017538003A (ja) 2017-12-21
SG11201704787QA (en) 2017-07-28
WO2016102341A1 (fr) 2016-06-30
MX2017007903A (es) 2017-09-05
US10308798B2 (en) 2019-06-04
CN107001733A (zh) 2017-08-01
RU2669370C1 (ru) 2018-10-11
IL252741A0 (en) 2017-07-31
AU2015371394B2 (en) 2017-10-26
PL3237533T3 (pl) 2019-02-28
EP3237533A1 (fr) 2017-11-01
CA2968647C (fr) 2018-05-22
SA517381711B1 (ar) 2021-04-19
BR112017011523B1 (pt) 2021-11-03
KR101944206B1 (ko) 2019-01-30
MY183316A (en) 2021-02-18
CA2968647A1 (fr) 2016-06-30
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